Accounts of Chemical Research最新文献

{"title":"Near-Infrared-II Fluorescent Probes for Analytical Applications: From In Vitro Detection to In Vivo Imaging Monitoring","authors":"Sha Liu,&nbsp;Wenhong Dong,&nbsp;Hui-quan Gao*,&nbsp;Zhaorui Song* and Zhen Cheng*,&nbsp;","doi":"10.1021/acs.accounts.4c0067110.1021/acs.accounts.4c00671","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00671https://doi.org/10.1021/acs.accounts.4c00671","url":null,"abstract":"<p >Biomarkers play a vital role in the regulation of life processes, especially in predicting the occurrence and development of diseases. For the early diagnosis and precise treatment of diseases, it has become necessary and significant to detect biomarkers with sensitivity, accuracy, simplicity, convenience, and even visualization. Fluorescent-probe-based techniques have been recognized as one of the most powerful tools for the sensitive detection and real time imaging of biomarkers in biological samples. However, traditional optical probes, mainly including the visible probes (400–700 nm) and the near-infrared I (NIR-I, 700–900 nm) probes, suffer from low sensitivity, poor resolution, strong absorption and scattering, and high background fluorescence, which hinder effective monitoring of biomarkers.</p><p >Fortunately, the past decade has witnessed a remarkable evolution in the application fields of near-infrared II (NIR-II, 900–1700 nm) fluorescence, driven by its exceptional optical characteristics and the advancement of imaging technologies. Leveraging the superior penetration capabilities, negligible autofluorescence, and extended fluorescence emission wavelengths, NIR-II fluorescent probes significantly enhance the signal-to-noise ratio (SNR) of <i>in vitro</i> detection (IVD) and the temporal resolution of <i>in vivo</i> imaging. Our team has been committed to the design strategy, controlled synthesis, luminous mechanisms, and biomedical applications of NIR-II fluorescent probes. In this Account, we present the representative works in recent years from our group in the field of NIR-II fluorescent probes for analytical applications, ranging from <i>in vitro</i> detection of biomarkers to <i>in vivo</i> imaging monitoring of different biomarkers and various diseases, which also will further provide a general overview of analytical applications of NIR-II fluorescence probes. First, the <i>in vitro</i> analytical applications of NIR-II fluorescent probes are fully summarized, including tumor marker detection, virus and bacteria analysis, cell testing, and small-molecule sensing. Second, the <i>in vivo</i> imaging monitoring applications of NIR-II fluorescent probes are adequately discussed, including ROS detection, gas monitoring, pH sensing, small-molecule testing, receptor analysis, and the imaging diagnosis of some serious diseases. Finally, we further outline the application advantages of NIR-II fluorescent probes in analytical fields and also discuss in detail some challenges as well as their future development. There is a reasonable prospect that the <i>in vitro</i> detection technology and the <i>in vivo</i> imaging monitoring technology based on NIR-II fluorescent probes will exhibit great development potential in biomedical research and clinical disease diagnosis. We hope that this Account can expand their reach into an even broader spectrum of fields, further enhancing their impact on scientific discovery and medical practice.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"543–554 543–554"},"PeriodicalIF":16.4,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Biological Polymers: Evolution, Function, and Significance","authors":"Kavita Matange,&nbsp;Eliav Marland,&nbsp;Moran Frenkel-Pinter and Loren Dean Williams*,&nbsp;","doi":"10.1021/acs.accounts.4c0054610.1021/acs.accounts.4c00546","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00546https://doi.org/10.1021/acs.accounts.4c00546","url":null,"abstract":"&lt;p &gt;A holistic description of biopolymers and their evolutionary origins will contribute to our understanding of biochemistry, biology, the origins of life, and signatures of life outside our planet. While biopolymer sequences evolve through known Darwinian processes, the origins of the backbones of polypeptides, polynucleotides, and polyglycans are less certain. We frame this topic through two questions: (i) Do the characteristics of biopolymer backbones indicate evolutionary origins? (ii) Are there reasonable mechanistic models of such pre-Darwinian evolutionary processes? To address these questions, we have established criteria to distinguish chemical species produced by evolutionary mechanisms from those formed by nonevolutionary physical, chemical, or geological processes. We compile and evaluate properties shared by all biopolymer backbones rather than isolating a single type. Polypeptide, polynucleotide, and polyglycan backbones are kinetically trapped and thermodynamically unstable in aqueous media. Each biopolymer forms a variety of elaborate assemblies with diverse functions, a phenomenon we call polyfunction. Each backbone changes structure and function upon subtle chemical changes such as the reduction of ribose or a change in the linkage site or stereochemistry of polymerized glucose, a phenomenon we call function-switching. Biopolymers display homo- and heterocomplementarity, enabling atomic-level control of structure and function. Biopolymer backbones access recalcitrant states, where assembly modulates kinetics and thermodynamics of hydrolysis. Biopolymers are emergent; the properties of biological building blocks change significantly upon polymerization. In cells, biopolymers compose mutualistic networks; a cell is an Amazon Jungle of molecules. We conclude that biopolymer backbones exhibit hallmarks of evolution. Neither chemical, physical, nor geological processes can produce molecules consistent with observations. We are faced with the paradox that Darwinian evolution relies on evolved backbones but cannot alter biopolymer backbones. This Darwinian constraint is underlined by the observation that across the tree of life, ribosomes are everywhere and always have been composed of RNA and protein. Our data suggest that chemical species on the Hadean Earth underwent non-Darwinian coevolution driven in part by hydrolytic stress, ultimately leading to biopolymer backbones. We argue that highly evolved biopolymer backbones facilitated a seamless transition from chemical to Darwinian evolution. This model challenges convention, where backbones are products of direct prebiotic synthesis. In conventional models, biopolymer backbones retain vestiges of prebiotic chemistry. Our findings, however, align with models where chemical species underwent iterative and recursive sculpting, selection, and exaptation. This model supports Orgel’s “gloomy” prediction that modern biochemistry has discarded vestiges of prebiotic chemistry. But there is ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 5","pages":"659–672 659–672"},"PeriodicalIF":16.4,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.accounts.4c00546","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143533986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Physical Phenomena in Porous Frameworks","authors":"Thomas Heine*,&nbsp;Mircea Dinca and Guangshan Zhou,&nbsp;","doi":"10.1021/acs.accounts.4c0083510.1021/acs.accounts.4c00835","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00835https://doi.org/10.1021/acs.accounts.4c00835","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 3","pages":"327–329 327–329"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Modeling of Electrocatalysts for CO₂ Reduction: Probing the Role of Primary, Secondary, and Outer Coordination Spheres.","authors":"Christina M Zeng, Julien A Panetier","doi":"10.1021/acs.accounts.4c00631","DOIUrl":"10.1021/acs.accounts.4c00631","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusIn the search for efficient and selective electrocatalysts capable of converting greenhouse gases to value-added products, enzymes found in naturally existing bacteria provide the basis for most approaches toward electrocatalyst design. Ni,Fe-carbon monoxide dehydrogenase (Ni,Fe-CODH) is one such enzyme, with a nickel-iron-sulfur cluster named the C-cluster, where CO&lt;sub&gt;2&lt;/sub&gt; binds and is converted to CO at high rates near the thermodynamic potential. In this Account, we divide the enzyme's catalytic contributions into three categories based on location and function. We also discuss how computational techniques provide crucial insight into implementing these findings in homogeneous CO&lt;sub&gt;2&lt;/sub&gt; reduction electrocatalysis design principles. The CO&lt;sub&gt;2&lt;/sub&gt; binding sites (e.g., Ni and \"unique\" Fe ion) along with the ligands that support it (e.g., iron-sulfur cluster) form the primary coordination sphere. This is replicated in molecular electrocatalysts via the metal center and ligand framework where the substrate binds. This coordination sphere has a direct impact on the electronic configuration of the catalyst. By computationally modeling a series of Ni and Co complexes with bipyridyl-&lt;i&gt;N&lt;/i&gt;-heterocyclic carbene ligand frameworks of varying degrees of planarity, we were able to closely examine how the primary coordination sphere controls the product distribution between CO and H&lt;sub&gt;2&lt;/sub&gt; for these catalysts. The secondary coordination sphere (SCS) of Ni,Fe-CODH contains residues proximal to the active site pocket that provide hydrogen-bonding stabilizations necessary for the reaction to proceed. Enhancing the SCS when synthesizing new catalysts involves substituting functional groups onto the ligand for direct interaction with the substrate. To analyze the endless possible substitutions, computational techniques are ideal for deciphering the intricacies of substituent effects, as we demonstrated with an array of imidazolium-functionalized Mn and Re bipyridyl tricarbonyl complexes. By examining how the electrostatic interactions between the ligand, substrate, and proton source lowered activation energy barriers, we determined how best to pinpoint the SCS additions. The outer coordination sphere comprises the remaining parts of Ni,Fe-CODH, such as the elaborate protein matrix, solvent interactions, and remote metalloclusters. The challenge in elucidating and replicating the role of the vast protein matrix has understandably led to a localized focus on the primary and secondary coordination spheres. However, certain portions of Ni,Fe-CODH's expansive protein scaffold are suggested to be catalytically relevant despite considerable distance from the active site. Closer studies of these relatively overlooked areas of nature's exceptionally proficient catalysts may be crucial to continually improve upon electrocatalysis protocols. Mechanistic analysis of cobalt phthalocyanines (CoPc) immobilized onto carbon nanotubes (CoPc/CN","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"342-353"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Using NMR Spectroscopy to Evaluate Metal-Ligand Bond Covalency for the f Elements.","authors":"Trevor W Hayton, Jochen Autschbach","doi":"10.1021/acs.accounts.4c00727","DOIUrl":"10.1021/acs.accounts.4c00727","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusUnderstanding f element-ligand covalency is at the center of efforts to design new separations schemes for spent nuclear fuel, and is therefore of signficant fundamental and practical importance. Considerable effort has been invested into quantifying covalency in f element-ligand bonding. Over the past decade, numerous studies have employed a variety of techniques to study covalency, including XANES, EPR, and optical spectroscopies, as well as X-ray crystallography. NMR spectroscopy is another widely available spectroscopic technique that is complementary to these more established methods; however, its use for measuring 4f/5f covalency is still in its infancy. This Account describes efforts in the authors' laboratories to develop and validate multinuclear NMR spectroscopy as a tool for studying metal-ligand covalency in the actinides and selected lanthanide complexes. Thus far, we have quantified M-L covalency for a variety of ligand types, including chalcogenides, carbenes, alkyls, acetylides, amides, and nitrides, and for a variety of isotopes, including &lt;sup&gt;13&lt;/sup&gt;C, &lt;sup&gt;15&lt;/sup&gt;N, &lt;sup&gt;77&lt;/sup&gt;Se, and &lt;sup&gt;125&lt;/sup&gt;Te. Using NMR spectroscopy to probe M-C and M-N covalency is particularly attractive because of the ready availability of the&lt;sup&gt;13&lt;/sup&gt;C and &lt;sup&gt;15&lt;/sup&gt;N isotopes (both &lt;i&gt;I&lt;/i&gt; = 1/2), and also because these elements are found in some of the most important f element ligand classes, including alkyls, carbenes, polypyridines, amides, imidos, and nitrides.The covalency analysis is based on the chemical shift (δ) and corresponding nuclear shielding constant (σ) of the metal-bound nucleus. The diamagnetic (σ&lt;sub&gt;dia&lt;/sub&gt;), paramagnetic (σ&lt;sub&gt;para&lt;/sub&gt;), and spin-orbit contributions (σ&lt;sub&gt;SO&lt;/sub&gt;) to σ can be obtained and analyzed by relativistic density functional theory (DFT). Of particular importance is σ&lt;sub&gt;SO&lt;/sub&gt;, which arises from the combination of spin-orbit coupling, the magnetic field, and chemical bonding. Its magnitude correlates with the amount of ligand s-character and metal &lt;i&gt;n&lt;/i&gt;f (and (&lt;i&gt;n&lt;/i&gt;+1)d) character in the M-L bond. In practice, Δ&lt;sub&gt;SO&lt;/sub&gt;, the total difference between calculated chemical shift for the ligand nucleus including vs excluding SO effects, provides a more convenient metric for analysis. For the examples discussed herein, Δ&lt;sub&gt;SO&lt;/sub&gt; accounts primarily for σ&lt;sub&gt;SO&lt;/sub&gt; in an f-element complex, but also includes minor SO effects on the other shielding mechanisms and (usually) minor SO effects on the reference shielding. Δ&lt;sub&gt;SO&lt;/sub&gt; can be very large, as in the case of [U(CH&lt;sub&gt;2&lt;/sub&gt;SiMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;6&lt;/sub&gt;] (348 ppm), which is not surprising as the An-C bonds in this example exhibits a high degree of covalency (e.g., 20% 5f character). However, even small values of Δ&lt;sub&gt;SO&lt;/sub&gt; can indicate profound bonding effects, as shown by our analysis of [La(C&lt;sub&gt;6&lt;/sub&gt;Cl&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;]&lt;sup&gt;-&lt;/sup&gt;. In this case, Δ&lt;sub&gt;SO&lt;/sub&gt; is only 9 ppm, ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"488-498"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES).","authors":"Cong Ma, Jian-Feng Guo, Shi-Shuo Xu, Tian-Sheng Mei","doi":"10.1021/acs.accounts.4c00656","DOIUrl":"10.1021/acs.accounts.4c00656","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with asymmetric transition metal catalysis. On one hand, we have rationalized that organometallic compounds can serve as molecular electrocatalysts (mediators) to reduce overpotentials and enhance both the reactivity and selectivity of reactions. On the other hand, the conditions for asymmetric transition metal catalysis can be substantially improved through electrochemistry, enabling precise modulation of the transition metal's oxidation state by controlling electrochemical potentials and regulating the electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional asymmetric transition metal catalysis, particularly those related to the use of redox-active chemical reagents. Furthermore, the redox potentials of molecular electrocatalysts can be conveniently tuned by modifying their ligands, thereby governing the reaction regioselectivity and stereoselectivity. As a result, the AOES has emerged as a powerful and promising tool for the synthesis of chiral compounds.In this Account, we summarize and contextualize our recent efforts in the field of AOES. Our primary strategy involves leveraging the controllability of electrochemical potential and current to regulate the oxidation state of organometallics, thereby facilitating the desired reactions. An efficient asymmetric synthesis platform was established under mild conditions, significantly reducing the reliance on chemical redox reagents. Our research has been systematically categorized into three sections based on distinct electrolysis modes: asymmetric transition metal catalysis combined with anodic oxidation, cathodic reduction, and paired electrolysis. In each section, we highlight our innovative discoveries tailored to the unique characteristics of the respective electrolysis modes.In many transformations, transition metal-catalyzed reactions involving traditional chemical redox reagents and those utilizing electrochemistry exhibit similar reactivities. However, we also observed notable differences in certain cases. These findings include the following: (1) Enhanced efficiency in asymmetric electrochemical synthesis: for instance, the Rh-catalyzed enantioselective electrochemical functionalization of C-H bonds demonstrates superior efficiency. (2) Expanded scope of transformations: certain transformations, previously challenging in traditional transition metal catalysis, can be achieved through electrochemistry due to the tunability of redox potentials. A notable example is the enantioselective reductive coupling of aryl chlorides, which significantly expands the range of accessible transformations. Additionally, our mechanistic studies explore unique techniques intrinsic to electrochemistry, such as controlled potential electrolysis experim","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"399-414"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystalline Covalent Triazine Frameworks and 2D Triazine Polymers: Synthesis and Applications.","authors":"Yumei Ren, Shuai Yang, Yuxi Xu","doi":"10.1021/acs.accounts.4c00729","DOIUrl":"10.1021/acs.accounts.4c00729","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusCovalent triazine frameworks (CTFs) are a novel class of nitrogen-rich conjugated porous organic materials constructed by robust and functional triazine linkages, which possess unique structures and excellent physicochemical properties. They have demonstrated broad application prospects in gas/molecular adsorption and separation, catalysis, energy conversion and storage, etc. In particular, crystalline CTFs with well-defined periodic molecular network structures and regular pore channels can maximize the utilization of the features of CTFs and promote a deep understanding of the structure-property relationship. However, due to the poor reversibility of the basic reaction for constructing the triazine unit and the traditional harsh synthesis conditions, it remains a considerable challenge to synthesize crystalline CTFs with diverse molecular structures, and there is still a significant lack of understanding of their polymerization mechanism, which limits their precise structural design, large-scale preparation, and practical applications. As the basic building block of bulk crystalline CTFs, two-dimensional triazine polymers (2D-TPs) which ideally have single-atom thickness have also aroused intensive interest due to their ultrathin 2D sheet morphology with structural flexibility, a fully exposed molecular plane and active sites, and excellent dispersibility and processability. However, the efficient and scalable production of high-quality 2D-TPs and the investigation of their unique properties and functions remain largely unexplored.In this Account, we summarize our recent contributions to the synthesis and application exploration of crystalline CTFs and 2D-TPs. We first introduce the design, synthesis, and polymerization mechanism of the crystalline CTFs. In order to synthesize high-quality CTFs, we have successively used a series of new synthetic methods including a solution polymerization strategy, microwave-assisted superacid-catalyzed polymerization strategy, polyphosphoric acid-catalyzed polymerization strategy, and solvent-free FeCl&lt;sub&gt;3&lt;/sub&gt;-catalyzed polymerization strategy, achieving the production of highly crystalline layered CTFs from the gram level to the hundred-gram level and then to the kilogram level and realizing new CTF molecular structures. We also reveal a direct ordered 2D polymerization mechanism that provided meaningful guidance for the controllable preparation of functional CTFs. Next, we introduce the design, synthesis, and formation mechanism of 2D-TPs. We have developed effective bottom-up and top-down strategies to prepare 2D-TPs for different needs. On one hand, we have established the dynamic interface polymerization method, the monomer-dependent method, and the solvent-free salt-catalyzed polymerization strategy for the direct synthesis of ultrathin 2D-TPs with thickness down to the single-layer limit and provided important insights into the 2D polymerization mechanism. On the other hand, we have","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"474-487"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microfluidics-Assembled Nanovesicles for Nucleic Acid Delivery","authors":"Xuanyu Li,&nbsp;Zhiliang Qin,&nbsp;Saijie Wang,&nbsp;Lingmin Zhang* and Xingyu Jiang*,&nbsp;","doi":"10.1021/acs.accounts.4c0073810.1021/acs.accounts.4c00738","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00738https://doi.org/10.1021/acs.accounts.4c00738","url":null,"abstract":"&lt;p &gt;Microfluidic technologies have become a highly effective platform for the precise and reproducible production of nanovesicles used in drug and nucleic acid delivery. One of their key advantages lies in the one-step assembly of multidrug delivery nanovesicles, which improves batch-to-batch reproducibility by minimizing the intermediate steps typically required in conventional methods. These steps often involve complex hydrophobic and electrostatic interactions, leading to variability in the nanovesicle composition and performance. Microfluidic systems streamline the encapsulation of diverse therapeutic agents, including hydrophilic nucleic acids, proteins, and both hydrophobic and hydrophilic small molecules, within a single chip, ensuring a more consistent production process. This capability enables the codelivery of multiple drugs targeting different disease pathways, which is particularly valuable in reducing the risk of drug resistance.&lt;/p&gt;&lt;p &gt;Despite the promise of nanovesicles for nucleic acid delivery, their clinical translation has been hindered by safety concerns, particularly cytotoxicity, which has overshadowed efforts to improve in vivo stability and delivery efficiency. Positively charged nanovesicles, commonly used to encapsulate negatively charged nucleic acids, tend to exhibit significant cytotoxicity. To address this, charge-shifting materials that respond to pH changes or surface modifications have been proposed as promising strategies. Shifting the surface charge from positive to neutral or negative at physiological pH can reduce the cytotoxicity, enhancing the clinical feasibility of these nanovesicle-based therapies.&lt;/p&gt;&lt;p &gt;Microfluidic platforms offer precise control over key nanovesicle properties, including particle size, rigidity, morphology, and encapsulation efficiency. Particle size is relatively easy to adjust by controlling flow rates within microfluidic channels, with higher flow rates generally producing smaller particles. However, continuous tuning of the particle rigidity remains challenging. By manipulation of the interfacial water layer between hydrophobic and amphiphilic components during nanoparticle formation, future designs may achieve greater control over rigidity, which is critical for improving cellular uptake and biodistribution. While shape tuning using microfluidic chips has not yet been fully explored in biomedical applications, advances in materials science may enable this aspect in the future, offering further customization of the nanovesicle properties.&lt;/p&gt;&lt;p &gt;The integration of nanovesicle assembly and surface modification within a single microfluidic platform presents challenges due to the differing speeds of these processes. Nanovesicle assembly is typically rapid, whereas surface modifications, such as those involving functional biomolecules, occur more slowly and often require purification steps. Recent advances, such as rotary valve designs and single-axis camshaft mechanisms, offer preci","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"570–582 570–582"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Physical Phenomena in Porous Frameworks.","authors":"Thomas Heine, Mircea Dinca, Guangshan Zhu","doi":"10.1021/acs.accounts.4c00835","DOIUrl":"10.1021/acs.accounts.4c00835","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 3","pages":"327-329"},"PeriodicalIF":16.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143121648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Indirect Construction of Chiral Metal–Organic Frameworks for Enantioselective Luminescence Sensing","authors":"Zongsu Han,&nbsp;Kun-Yu Wang,&nbsp;Mengmeng Wang and Wei Shi*,&nbsp;","doi":"10.1021/acs.accounts.4c0079510.1021/acs.accounts.4c00795","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00795https://doi.org/10.1021/acs.accounts.4c00795","url":null,"abstract":"&lt;p &gt;Chiral metal–organic frameworks (MOFs) are promising candidates as luminescent sensing materials for chiral species, which are essential components in modern industries, pharmaceuticals, and biological processes. The discrimination of enantiomers with highly similar physical and chemical properties is crucial because they are often present concurrently in the same system but may feature distinct effects on living matters. While the rapid and precise sensing capabilities of chiral MOFs outshine traditional detection methods for chiral species in daily life, chemical production, and the natural environment, it requires well-matched chemical and electronic structures between MOFs and chiral species. Yet, conventional strategies to construct chiral luminescent MOFs are immensely challenging due to the crystallization difficulties based on low-symmetric building blocks.&lt;/p&gt;&lt;p &gt;Recent advancements in MOF chemistry have led to novel pathways for synthesizing chiral MOFs for enantioselective sensing. Compared with direct synthesis using optically pure luminescent ligands, which are usually complex and costly, indirect synthesis has garnered significant attention for reduced costs, simplified synthesis, enhanced material stability, and broad application scope. In the past few years, our group has developed chiral guest ion exchange, chiral coordination modification, and chiral defect engineering for indirectly synthesizing chiral MOFs. The chiral guest ion exchange is cost-effective for introducing chiral ions into MOF pores but can be applied only in charged frameworks. In addition, it also faces limitations in chiral ion availability and the tendency toward chirality loss during the sensing process. Besides, compared with ion exchange, the chiral coordination modification can maintain the chemical stability of chiral MOFs due to the stronger coordination bonds. Still, it requires MOFs with accessible open metal sites that may bind disordered dangling molecules, complicating structural determination. Therefore, specific pathways such as chiral linker installation with dual-end coordination have been developed to afford well-defined crystal structures. While all aforementioned methods may decrease the MOFs’ pore sizes to a certain degree, we further developed a chiral defect engineering approach to enlarge pore size and introduce chiral center simultaneously. Such a highly competitive strategy is facile and low-cost and can be expanded to many well-known stable MOFs.&lt;/p&gt;&lt;p &gt;In this Account, we delve into the intricate evolution of indirect strategies for constructing chiral MOFs tailored for enantioselective sensing applications. We provide a detailed analysis of the progression and innovation within the field, tracing the development of MOF-based enantioselective luminescence sensors. By systematically reviewing the various synthetic approaches, this work highlights their respective strengths and limitations. Beyond reviewing the state of the art","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"625–634 625–634"},"PeriodicalIF":16.4,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}